Hair dye composition and method of dyeing human hair therewith

ABSTRACT

IN WHICH R1 IS A LOWER ALKYL HAVING 1-4 CARBON ATOMS AND A- IS AN ANION, AND THE METHOD OF DYEING HUMAN HAIR WITH THIS COMPOSITION.   1-HO,2,4-DI((4-(R1-N(-CH3)2-)PHENYL)-NH-)ANTHAQUINONE   A HAIR DYE COMPOSITION COMPRISING A SOLVENT AND A QUATERNARY AMMONIUM SALT HAVING THE FORMULA

United States Patent 3,692,461 HAIR DYE COMPOSITION AND METHOD OF DYEINGHUMAN HAIR THEREWITH Gregoire Kalopissis, Paris, Jack Bertrand,Tremblay-les- Gonesses, and Andree Bugant, Bologne-sur-Seine, France,assignors to Societe Anonyme ditc, lOreal, Paris, France No Drawing.Continuation-impart of application Ser. No. 428,867, Jan. 28, 1965. Thisapplication May 15, 1970, Ser. No. 37,903 Claims priority, applicationFrance, Feb. 5, 1964,

- 962,659, Patent 1,430,091

Int. Cl. D06p 3/00 U.S. Cl. 810 6 Claims ABSTRACT OF THE DISCLOSURE Ahair dye composition comprising a solvent and a quaternary ammonium salthaving the formula in which R is a lower alkyl having 1-4 carbon atomsand A- is an anion, and the method of dyeing human hair with thiscomposition.

0 OH H- A CH3 CH: e

in which R, is a lower alkyl having 1-4 carbon atoms (for instance amethyl, ethyl, propyl or butyl radical); and A- is an anion, such as ahalogen, such as Cl, Br and I or a methylsulphate ion.

Examples of two compounds falling within the scope of theabove-indicated Formula I are: methyl-[l-hydroxy- 2,4bis-(p-trimethylammonium-phenyl)aminoanthraquinone] sulphate, that isthe compound of Formula I where R is methyl and A- is methylsulphate,and [l-hydroxy- 2,4 bis (p trimethylammoniumphenyl)aminoanthraquinone]iodide, that is the compound of Formula I where R, is methyl and A- isiodide.

The quaternary salts of this invention when applied to human hair giveattractive grey shades of great intensity ice for which there is need inthe art of hair-dyeing. They also have the advantage that they are verysoluble in water over a very wide pH range, the aqueous solutionsobtained being, in general, tolerant of all the practical conditionsunder which hair dyeing is carried out. Moreover, the quaternary saltswhen applied to hair have a high resistance to sunlight, which is a mostvaluable property for hair dyes, and they also well withstand thepresence of ingredients generally incorporated in dyeing compositions,such as hair penetrating and swelling agents, lustreproducing productsand thickening agents.

1 hydroxy 2,4-bis (p-dimethylaminophenyl)aminoanthraquinone can beobtained by the reaction of N,N-dimethyl-p-phenylenediamine withpurpurin, that is, 1,2,4- trihydroxyanthraquinone. The quaternary saltsof l-hydroxy 2,4 bis(p-dimethylaminophenyl)aminoanthraqu-inone can beobtained by reacting the latter compound with a quaternizing agent suchas methyl iodide or methyl sulphate.

The invention also relates to a method of dyeing keratinic fibers, moreparticularly hair, by applying to the fibers a quaternary salt of thisinvention, allowing sufiicient time to elapse for the said compound toexert its dyeing effect and then removing any unwanted excess of thecompound from the hair. The quaternary salt is conveniently used in theform of an aqueous solution that is left in contact with the hair forabout 15 to 60 minutes at ambient temperature, after which the hair isrinsed and washed.

The dyeing compositions suitable for dyeing keratinic fibers may takethe form of solutions, emulsions, gels or creams, containing aquaternary salt of this invention. The dyeing compositions of thisinvention have a pH value of approximately 3 to 9.

The dye compositions of the invention may be used in combination withother dyestuffs which may or may not be quaternary salts of thisinvention or belong to the family of the antraquinone dyestuffs.

The invention is illustrated by the following examples.

EXAMPLE I Preparation of l-hydroxy-2,4-bis (p-dimethylaminophenyl)aminoanthraquinone There is heated for 8 hours at C. a mixtureconsisting of 264 g. of industrial purpurin, 64 g. of boric acid and1018 g. of N,N-dimethyl(p-phenylenediamine), whereafter the mixture isdiluted with 1.5 liters of alcohol and 3 liters of water. The crudeproduct is thereafter separated and recrystallized from chlorobenzene.The product thus obtained has a melting point of 254255 C. and thefollowing analysis:

Calculated (percent): C, 73.17; H, 5.69; N, 11.38. Found (percent): C,73.65-73.37; H, 5.80-5.72; N, 11.56-11.22.

EXAMPLE II Preparation ofmethyl-[1-hydroxy-2,4-bis(p-trimethylammoniumphenyl)-aminoanthraquinone]sulphate This compound is obtained by the action of 11.4 g. of methylsulphate on a solution of 20 g. of 1-hydroxy-2,4-bis(p-dimethylaminophenyl)aminoanthraquinone in 200 cc. of benzene. Thequaternary ammonium obtained is separated, and it melts withdecomposition at 200-203 C.

EXAMPLE III Preparation of[l-hydroxy-2,4-bis(p-trimethylammoniumphenyl)aminoanthraquinone] iodideThis compound is obtained by the action of methyl iodide (2.14 g.) onl-hydroxy-ZA-(p-dimethylaminophenyl)aminoanthraquinone (3.32 g.). Itdecomposes at 260 C.

3 EXAMPLE IV A dyeing solution according to the invention is prepared bymixing:

Methyl [1 hydroxy 2,4 bis( p trimethyammoniumphenyl) aminoanthraquinone]sulphate, g. Sodium carbonate, q.s. for pH 7 Water, q.s. for 1000 cc.

This solution is applied to 100% white hair and left in contacttherewith for 20 minutes at ambient temperature, whereafter the hair iswashed, rinsed and dried.

The coloration thus obtained in the hair is violet-grey.

EXAMPLE V A dyeing solution according to the invention is prepared bymixing:

[ l-hydroxy-2,4-bis (p-trimethylammoniumphenyl) -aminoanthraquinone]iodide, 10 g. Sodium carbonate, q.s. for pH 7 Water q.s. for 1000 cc.

This solution is applied to 100% white hair and left in contacttherewith for 20 minutes at ambient temperature, whereafter the hair isrinsed, shampooed, rinsed again and dried.

The coloration thus obtained in the hair is blue-grey.

EXAMPLE VI A solution according to the invention is prepared by mixing:

G. Methyl [4 hydroxy l (B-methylmorpholinium)- ethylaminoanthraquinone]sulphate 1.4 1 ('y dimethylaminopropyl) amino 2 amino-4- nitrobenzenemonohydrochloride 2.8 Methyl [1hydroxy-2,4-bis(p-trimethylammoniumphenyl) aminoanthraquinone] sulphate8.5

Methyl [1,5 bis(,8 methylmorpholinium)ethylaminoanthraquinone] sulphate8.5

Sodium carbonate, q.s. for pH 8.5. Water, q.s. for 1000 cc.

When applied to light chestnut-colored hair and left for minutes thismixture imparts a pearly-red tinge to the hair, after washing, rinsingand drying.

EXAMPLE VH A dyeing solution according to the invention is prepared bymixing:

N-monomethylnitro-p-phenylenediamine 6.5 1 ('y dimethylaminopropyl)amino 2-amino-4- nitrobenzene monohydrochloride 12 Methyl [l-hydroxy 2,4bis(p-trimethylammoniumphenyl)aminoanthraquinone] sulphate 2 Methyl [1,4bis(B-methylmorpholinium)ethylaminoanthraquinone] sulphate 6 Sodiumcarbonate, q.s. for pH 8.5. Water, q.s. for 1000 cc.

This mixture, when applied to natural light-brown hair comprising 30% ofwhite hair and left for 15 minutes, im-

[1-hydroxy-2,4-bis(p-propyl, dimethylammoniumphenyl) aminoanthraquinone]chloride [l-hydroXy-2,4-bis(p-ethyi, dimethlylammoniumphenyl)aminoanthraquinone] bromide and l-hydroxy-2,4-bis(p-butyldimethylammoniumphenyl aminoanthraquinonel iodide.

What is claimed is:

1. A dye composition suitable for dyeing human hair comprising asolution of a quaternary salt of l-hydroxy- 2,4 bis(pdimethyl-aminophenyl)aminoanthraquinone of the formula:

in which R is a lower alkyl having 1-4 carbon atoms and A- is selectedfrom the group consisting of halides and methyl sulphate, having a pH ofapproximately 3 to 9.

2. The dye composition of claim 1 wherein said R is methyl.

3. The dye composition of claim 1 wherein said salt is methyl [1hydroxy-2,4-bis(p-trimethylammoniumphenyl) aminoanthraquinone sulphate.

4. The dye composition of claim 1 wherein said salt is {1 hydroxy 2,4bis(p-trimethylammoniumphenyl) aminoanthraquinone] iodide.

5. The composition of claim 1, in which A- is selected from the groupconsisting of chloride, bromide and iodide.

6. Method of dyeing human hair which comprises applying to hair a dyecomposition of claim 1, leaving said dye composition in contact withsaid hair for about 15 to minutes at ambient temperature andsubsequently removing excess dye composition from said hair.

References Cited UNITED STATES PATENTS 3,004,974 10/1961 Grossmann eta1. 260-279 3,531,502 9/1970 Kalopissis et a1. 260-380 GEORGE F. LESMES,Primary Examiner T. I. HERBERT, IR., Assistant Examiner US. Cl. X.R.260-380

